Bimetallic nanostructures are promising candidates for the development of enzyme‐mimics, yet the deciphering of the structural impact on their catalytic properties poses significant challenges. By leveraging the structural versatility of nanocrystal aerogels, this study reports a precise control of Au–Pt bimetallic structures in three representative structural configurations, including segregated, alloy, and core–shell structures. Benefiting from a synergistic effect, these bimetallic aerogels demonstrate improved peroxidase‐ and glucose oxidase‐like catalytic performances compared to their monometallic counterparts, unleashing tremendous potential in catalyzing the glucose cascade reaction. Notably, the segregated Au–Pt aerogel shows optimal catalytic activity, which is 2.80 and 3.35 times higher than that of the alloy and core–shell variants, respectively. This enhanced activity is attributed to the high‐density Au–Pt interface boundaries within the segregated structure, which foster greater substrate affinity and superior catalytic efficiency. This work not only sheds light on the structure–property relationship of bimetallic catalysts but also broadens the application scope of aerogels in biosensing and biological detections.